(1) Field of the Invention
This invention relates to medium set mixing grade asphalt emulsions, rapid set emulsions and quick set slurry seal emulsions. More particularly, it relates to novel emulsifiers for solventless and solvent containing mixing grade, oil-in-water anionic and cationic bituminous emulsions, which emulsifiers are the reaction products of polyamines with certain polycarboxylic acid anhydrides and their modified products. Modifications are carried out by reacting the nitrogen-containing intermediates with formaldehyde and sodium sulfite or bisulfite, haloalkane sulfonic acid salts, .gamma.-propane sultone, halomethane phosphonic acid, acrylic acid, fumaric acid, maleic acid and haloalkanoic acids.
(2) Description of the Prior Art
In paving operations, three main practices are employed to achieve thorough mixing of bitumen and aggregate:
(1) mixing of free flowing heated asphalt (asphalt cement) with pre-dried aggregate; PA0 (2) mixing pre-dried aggregate with asphalt diluted with a hydrocarbon solvent (cutback asphalt, cutter stock) at ambient temperatures; and PA0 (3) mixing aggregate with asphalt emulsions, e.g., oil-in-water emulsions, obtained by vigorous agitation of asphalt and water in the presence of an emulsifying agent. PA0 (a) formaldehyde and sodium sulfite or bisulfite EQU &gt;NH+CH.sub.2 O+NaHSO.sub.3 .fwdarw.&gt;NCH.sub.2 SO.sub.3 Na PA0 (b) halo-alkane sulfonic acid sodium salts ##STR7## (c) .gamma.-propane sultone ##STR8## (d) chlorohydroxypropane sulfonic acid sodium salt ##STR9## (e) haloalkanoic acids (or sodium salts) ##STR10## (f) .alpha.,.beta.-unsaturated carboxylic or dicarboxylic acids: ##STR11## (g) haloalkane phosphonic acids EQU &gt;NH+X(CH.sub.2).sub.n PO.sub.3 H.sub.2 .fwdarw.&gt;N(CH.sub.2).sub.n PO.sub.3 H.sub.2 PA0 (h) formaldehyde and phosphorous acid in the presence of hydrochloric acid EQU &gt;NH+CH.sub.2 O+H.sub.3 PO.sub.3 .fwdarw.&gt;NCH.sub.2 PO.sub.3 H.sub.2
Because of increasing cost in energy and hydrocarbon solvents and because of environmental concerns, the use of emulsified asphalt is increasing. Dependent on the emulsifier used to achieve an emulsion, anionic or cationic emulsions are obtained. In anionic emulsions, asphalt droplets are negatively charged; in cationic emulsions, the asphalt droplets bear positive charges and migrate to the cathode when an electric field is applied.
Generally, depending on the characteristics of the type of mixing and rate of break, bituminous emulsions are classified as rapid setting, medium setting and slow setting. In the case of rapid setting emulsions, mainly used for repair work of old wearing courses, the emulsion is applied on the existing surface and aggregate is spread on top, and after compaction, the road can be opened to traffic shortly after the application of the new coat (chip seal, etc.). Medium setting emulsions are mixed with aggregate prior to being used in road construction, and slow set emulsions can be mixed with aggregate and stored for a longer period of time without breaking on the aggregate surface.
Anionic bituminous emulsions are taught by Wright and Mertens in U.S. Pat. No. 3,062,829 to be prepared by employing alkali emulsifier and polyamide additives which are the condensation products of dilinoleic acid and polyalkylene polyamines. Lignin amines are taught as anionic emulsifiers in U.S. Pat. No. 3,123,569 to Borgfeldt. Also, Moorer, in U.S. Pat. No. 3,956,002, teaches an anionic emulsifier consisting of an oxygenated alkali lignin, an ethylene oxide adduct of alkyl-phenol, and up to 10% by weight of sodium borate; and, in U.S. Pat. No. 4,088,505, he teaches an anionic emulsifier consisting of an alkali metal salt of an alkali lignin, an ethylene oxide adduct of alkyl-phenol and water. In addition, Montgomery and Pitchford teach the alkali metal salts of complex polynuclear aromatic polycarboxylic acids as anionic asphalt emulsifiers in U.S. Pat. No. 3,344,082. Heinz, in U.S. Pat. No. 3,006,860, similarly employs alkali metal soaps of higher fatty acids as those found in tall oil.
Ferm, in U.S. Pat. No. 3,740,344, teaches the preparation of quick-setting anionic slurry seal compositions by applying a combination of anionic emulsifiers such as aryl alkyl sulfonates and condensation products of ethylene oxide with alkylated phenols, with fatty alcohols, with mono-esters of fatty acids with glycerol or sorbitol or long chain fatty acids. H. G. Schreuders, in U.S. Pat. No. 3,615,796, teaches the use of petroleum sulfonates as quick-setting anionic slurry seal emulsifiers. A combination of sodium lignate or lignosulfonate and saponified rosin or tall oil is described in U.S. Pat. No. 3,594,201 by Sommer and Evans. Also, Conn, in U.S. Pat. No. 3,350,321, describes the use of alkyl or alkoxyalkyl phosphoric acids as emulsifiers for asphalts.
Cationic emulsions are obtained by employing a variety of nitrogen containing organic compounds, such as fatty amines, fatty diamines, fatty triamines, fatty amidoamines, fatty imidazolines, and reaction products of all these compounds with ethylene oxide and fatty mono- and diquaternary ammonium salts. The fatty radical of these compounds can have a variety of chemical structures, and the building blocks for the preparation of these amines can be obtained from a variety of sources, such as petroleum refinates, animal fats, vegetable and fish oils, and tall oil. Amidoamines suitable as emulsifiers are disclosed in U.S. Pat. No. 3,230,104 to Falkenberg and in U.S. Pat. No. 3,097,174 to Mertens. Combinations of fatty monoamines and triamines are disclosed in U.S. Pat. No. 3,738,852 to Doi; fatty diamines are disclosed in U.S. Pat. No. 3,728,278 to Tramelli and U.S. Pat. No. 3,581,101 to Gzemski; fatty quaternary and diquaternary salts and modifications thereof are disclosed in U.S. Pat. No. 3,220,953 to Borgfeldt, U.S. Pat. No. 3,867,162 to Elste, U.S. Pat. No. 3,764,359 to Dybalski, U.S. Pat. No. 3,957,524 to Doughty and U.S. Pat. No. 3,466,247 to Ohtsuka, and fatty imidazolines are taught in U.S. Pat. No. 3,445,258 to Ferm.
Generally, asphalt emulsions prepared with fatty amines, fatty diamines, fatty amidoamines, etc., are unstable when mixed with a variety of siliceous or calcareous aggregates. Rapid breaking on the aggregate surface is observed with an increase in stiffening. At this point, the mix becomes unworkable. To overcome this problem, it is common practice to use cutback asphalt instead of asphalt cement for medium set mixing grade asphalt emulsions. Although cutback emulsions prepared with these emulsifiers also break when mixed with the aggregate, the solvent (a hydrocarbon oil, such as naphtha, kerosene, diesel oil, etc.) decreases the viscosity of the asphalt and increases the workability of the aggregate-asphalt mix. After placement of the mixes, the solvent evaporates and the final stiff aggregate-asphalt matrix is obtained. Because of the dramatically increased cost of solvents in recent years and because of the effort to reduce pollution, suitable emulsifiers are sought for mixing grade emulsions without using solvent. The use of tallow quaternary ammonium salts and tallow diquaternary diammonium salts for making emulsions suitable for slurry seal, a solventless application, is described in U.S. Pat. No. 3,764,359 to Dybalski, and the use of a quaternary amine obtained by reacting epichlorohydrin, trimethylamine and nonylphenol for solventless mixes is disclosed in U.S. Pat. No. 3,957,524 to Doughty.
In U.S. Pat. No. 4,447,269, an aqueous bituminous emulsion fine-grained aggregate slurry mixture is disclosed which deposits at a fairly rapid rate after being applied to the surface to be treated, and is usable for a longer periof of time to enable application in slurry form. The disclosed cationic quick setting and solventless medium setting asphalt emulsion is formed with an emulsifier which is the product of the reaction of a polyamine with a polycarboxylic acid of the general formula ##STR1## wherein x and y are integers from 3 to 9, x and y together equal 12, at least one Z is a carboxylic acid group and any remaining Z is hydrogen. The rate of setting is determined by emulsifier dosage, pH, aggregate gradation and temperature.
The general object of this invention is to provide novel versatile emulsifiers for solventless and solvent containing rapid setting and medium setting mixing grade, oil-in-water bituminous emulsions. Another object of this invention is to provide emulsifier formulations for mixing grade emulsions which give a variety of set times as expressed in percent initial washoff coating (the percent coat on the aggregate surface after one minute mixing and immediate immersion in water) and percent one hour washoff coating. A further object of this invention is to provide new amidoamines, imidoamines or imidazolines, and amphoteric derivatives prepared by reacting polycarboxylic acid anhydrides with polyamines and by modifying these products with a variety of reagents such as formaldehyde and sodium sulfite or bisulfite, haloalkane sulfonic acid sodium salts, .gamma.-propane sultone, chlorohydroxy propane sulfonic acid sodium salt, vinyl sulfonic acid sodium salt, haloalkanoic acids, such as chloroacetic acid, .alpha.,.beta.-unsaturated carboxylic acids, such as acrylic, metacrylic, fumaric and maleic acid, epoxy carboxylic acids, halo alkane phosphoric acids, formaldehyde and phosphorous acid in the presence of hydrochloric acid, suitable as emulsifiers for both anionic and cationic oil-in-water emulsions. From the literature, it is known that these reagents react with the active nitrogens of amines in Mannich type reactions, by Michael additions or by nucleophilic substitution yielding amino alkyl-sulfonic acids, and amino alkyl carboxylic acids (amino acids). These products are amphoteric. They are soluble at both acidic and alkaline pH-values, and at the isoelectric point, where the number of positive charges equals the number of negative charges on the molecule, they do not move when an electrical field is applied, and they show reduced solubility in water.